US3025316A - Thiophosphoric acid esters and a process for their production - Google Patents

Thiophosphoric acid esters and a process for their production Download PDF

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Publication number
US3025316A
US3025316A US846066A US84606659A US3025316A US 3025316 A US3025316 A US 3025316A US 846066 A US846066 A US 846066A US 84606659 A US84606659 A US 84606659A US 3025316 A US3025316 A US 3025316A
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Prior art keywords
acid esters
thiophosphoric acid
production
mercaptomethyl
fluorophenyl
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Expired - Lifetime
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US846066A
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Lorenz Walter
Schrader Gerhard
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal

Definitions

  • the present invention relates to and has as its objects new and useful insecticidal thiophosphoric acid esters and their production. Generally the new compounds may be represented by the following formula in which R stands for lower alkyl radicals.
  • Fluorophenyl mercaptomethyl dithiophosphoric acid esters are known already from the literature. However, the corresponding monothiophosphoric acid esters are not described as yet and it has been found that this new class of compounds has a particularly good insecticidal action which exceeds that of the known dithiophosphoric acid esters whilst the toxicity is comparatively low.
  • the new compounds are obtained in a manner known in principle, e.g. by reaction of the corresponding fluorophenyl-mercaptomethyl halides with salts of 0.0-dialkylthiolphosphoric acids, as it is to be seen from the following equation:
  • the reaction is preferably carried out in the presence of inert diluents such as alcohols, lower ketones, benzene, toluene and the like, and at a slightly elevated temperature.
  • inert diluents such as alcohols, lower ketones, benzene, toluene and the like
  • the new compounds are applied in a manner known in principle: that is to say in combination with solid or liquid extenders or diluents.
  • Chalk, talc, bentonite, kieselguhr nd the like have chiefly proved to be useful as such exten ers.
  • liquid combinations should preferably consist of aqueous emulsions which are easily obtainable from the above mentioned compounds with the use of suitable auxiliary solvents and commercial emulsifiers.
  • ester of the following formula has been tested against spider mites (systemic action).
  • Aqueous solutions of the aforesaid compound have been prepared by admixing them with the same amount of an auxiliary solvent (acetone).
  • a commercial emulsifier (benzyl hydroxy diphenyl polyglycol ether) is added in an amount of 20% referred to active ingredient. This premixture then is diluted with water to the desired concentration.
  • esters of the following formulae By the same way but using instead of the ammonium salt of diethyl-thiolphosphoric acid the corresponding equimolecular amount of dimethylor diisopropyl-thiolphosphoric acid there are obtained the esters of the following formulae:

Description

llnited States Eatent 3,025,316 THKOPHOSPHGRIC ACID ESTERS AND A PROCESS FER T HEllR PRODUCTTQN Walter Lorenz, Wnppertal-Vohwinkel, and Gerhard Schrader, Wnppertal-Cronenherg, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Lever-kusen, Germany, a corporation of Germany No Drawing. Filed Oct. 13, 1959, Ser. No. 846,066 Claims priority, application Germany Oct. 18, 1958 r 4 Claims. (Cl. 260-461) The present invention relates to and has as its objects new and useful insecticidal thiophosphoric acid esters and their production. Generally the new compounds may be represented by the following formula in which R stands for lower alkyl radicals.
Fluorophenyl mercaptomethyl dithiophosphoric acid esters are known already from the literature. However, the corresponding monothiophosphoric acid esters are not described as yet and it has been found that this new class of compounds has a particularly good insecticidal action which exceeds that of the known dithiophosphoric acid esters whilst the toxicity is comparatively low.
The new compounds are obtained in a manner known in principle, e.g. by reaction of the corresponding fluorophenyl-mercaptomethyl halides with salts of 0.0-dialkylthiolphosphoric acids, as it is to be seen from the following equation:
OCH;
O OOH OOHg The reaction is preferably carried out in the presence of inert diluents such as alcohols, lower ketones, benzene, toluene and the like, and at a slightly elevated temperature.
The new compounds are applied in a manner known in principle: that is to say in combination with solid or liquid extenders or diluents. Chalk, talc, bentonite, kieselguhr nd the like have chiefly proved to be useful as such exten ers. If liquid combinations are to be applied, they should preferably consist of aqueous emulsions which are easily obtainable from the above mentioned compounds with the use of suitable auxiliary solvents and commercial emulsifiers.
As an example for the special utility of the inventive compounds the ester of the following formula has been tested against spider mites (systemic action). Aqueous solutions of the aforesaid compound have been prepared by admixing them with the same amount of an auxiliary solvent (acetone). A commercial emulsifier (benzyl hydroxy diphenyl polyglycol ether) is added in an amount of 20% referred to active ingredient. This premixture then is diluted with water to the desired concentration.
The test has been carried out as follows: Bean plants of about 7 inches height (Phaseolus vulgaris) in pots of about inches diameter are watered with 250 millilitres of an aqueous emulsion as prepared above in a concen- 3,025,316 Patented Mar. 13, 1962 ice Example 56 grams (0.3 mol) of the ammonium salt of diethylthiolphosphoric acid and 44 grams (0.25 mol) of 4- fluorophenyl-mercaptomethyl chloride (13.1. 43 C./0.0l mm. Hg) are warmed in 150 cc. of n-propyl alcohol to 6070 C. for two hours with stirring. After cooling, the reaction product is poured into water and the precipitated oil taken up with benzene. After washing with water and a sodium bicarbonate solution, the solvent is dried and distilled off. The residual oil grams) distils after slight first runnings at 109 C./ 0.01 mm. Hg as a pale yellow oil. Yield: 65 grams corresponding to 93.6% of the theoretical.
By the same way but using instead of the ammonium salt of diethyl-thiolphosphoric acid the corresponding equimolecular amount of dimethylor diisopropyl-thiolphosphoric acid there are obtained the esters of the following formulae:
We claim:
1. S (fluorophenyl mercaptomethyl) 0.0 di lower-alkylphosphoric acid esters in which the alkyl group contains up to 4 carbon atoms.
2. The thiophosphoric acid ester of the following formula 3. The thiophosphoric acid ester of the following formula 4. The thiophosphoric acid ester of the following formula References Cited in the file of this patent UNITED STATES PATENTS 2,597,534 Schrader May 20, 1952 2,793,224 Fancher May 21, 1957 2,852,549 Crrover et al. Sept. 16, 1958 2,891,984 Gatzi et al. June 23, 1959 FOREIGN PATENTS 772,213 Great Britain Apr. 10, 1957 1,016,260 Germany Sept. 26, 1957

Claims (1)

1. S - (FLUOROPHENYL - MERCAPTOMETHYL) - OO - DI LOWER-ALKYLPHOSPHORIC ACID ESTERS IN WHICH THE ALKYL GROUP CONTAINS UP TO 4 CARBON ATOMS.
US846066A 1958-10-18 1959-10-13 Thiophosphoric acid esters and a process for their production Expired - Lifetime US3025316A (en)

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DEF0026849 1958-10-18

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US3025316A true US3025316A (en) 1962-03-13

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US (1) US3025316A (en)
BE (1) BE583685A (en)
CH (1) CH399441A (en)
DE (1) DE1071696B (en)
DK (1) DK104029C (en)
FR (1) FR1237651A (en)
GB (1) GB874570A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408324A (en) * 1966-12-27 1968-10-29 Nat Distillers Chem Corp Stabilizing organic materials
US3413258A (en) * 1966-10-20 1968-11-26 Nat Distillers Chem Corp Enhancement of resistance of olefin polymers to heat deterioration
US3449473A (en) * 1966-08-03 1969-06-10 Du Pont Hydrocarbyl and hydrocarbylene monoand bis(phosphorodifluorido)dithioate esters
US3462530A (en) * 1964-06-12 1969-08-19 Stauffer Chemical Co S-chlorophenoxy-methyl,thio,dithio phosphonates or phosphates as insecticides and acaricides
CN114411180A (en) * 2022-03-08 2022-04-29 江西师范大学 Method for constructing sulfur (selenium) substituted phosphate compound by electrochemical hydrogen-releasing oxidation coupling
CN114525529A (en) * 2022-03-08 2022-05-24 江西师范大学 Method for constructing sulfur (selenium) substituted thioester phosphate compound by electrochemical hydrogen-releasing oxidation coupling

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1137006B (en) * 1960-02-18 1962-09-27 Geigy Ag J R Process for the preparation of the insecticidally active S-phenyl-mercaptomethyl-O, O-dimethyl-dithiophosphoric acid ester

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2597534A (en) * 1949-05-07 1952-05-20 Bayer Ag Neutral esters of thiolphosphoric acid
GB772213A (en) * 1954-06-10 1957-04-10 Geigy Ag J R Improvements in and relating to dithiophosphoric acid esters
US2793224A (en) * 1954-02-03 1957-05-21 Stauffer Chemical Co P-chlorophenyl-mercaptomethyl di-alkyl dithiophosphates and their use as insecticides
DE1016260B (en) * 1956-03-09 1957-09-26 Bayer Ag Process for the production of O, O-dialkyl-thiol-phosphoric acid-S-mercaptomethyl-triesters
US2852549A (en) * 1956-02-14 1958-09-16 Eastman Kodak Co Preparation of neutral mixed phosphates by interaction of phosphates

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2597534A (en) * 1949-05-07 1952-05-20 Bayer Ag Neutral esters of thiolphosphoric acid
US2793224A (en) * 1954-02-03 1957-05-21 Stauffer Chemical Co P-chlorophenyl-mercaptomethyl di-alkyl dithiophosphates and their use as insecticides
GB772213A (en) * 1954-06-10 1957-04-10 Geigy Ag J R Improvements in and relating to dithiophosphoric acid esters
US2891984A (en) * 1954-06-10 1959-06-23 Geigy Ag J R New dithiophosphoric acid esters and their use for the control of mites
US2852549A (en) * 1956-02-14 1958-09-16 Eastman Kodak Co Preparation of neutral mixed phosphates by interaction of phosphates
DE1016260B (en) * 1956-03-09 1957-09-26 Bayer Ag Process for the production of O, O-dialkyl-thiol-phosphoric acid-S-mercaptomethyl-triesters

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3462530A (en) * 1964-06-12 1969-08-19 Stauffer Chemical Co S-chlorophenoxy-methyl,thio,dithio phosphonates or phosphates as insecticides and acaricides
US3449473A (en) * 1966-08-03 1969-06-10 Du Pont Hydrocarbyl and hydrocarbylene monoand bis(phosphorodifluorido)dithioate esters
US3413258A (en) * 1966-10-20 1968-11-26 Nat Distillers Chem Corp Enhancement of resistance of olefin polymers to heat deterioration
US3408324A (en) * 1966-12-27 1968-10-29 Nat Distillers Chem Corp Stabilizing organic materials
CN114411180A (en) * 2022-03-08 2022-04-29 江西师范大学 Method for constructing sulfur (selenium) substituted phosphate compound by electrochemical hydrogen-releasing oxidation coupling
CN114525529A (en) * 2022-03-08 2022-05-24 江西师范大学 Method for constructing sulfur (selenium) substituted thioester phosphate compound by electrochemical hydrogen-releasing oxidation coupling
CN114525529B (en) * 2022-03-08 2023-03-10 江西师范大学 Method for constructing sulfur (selenium) substituted thioester phosphate compound by electrochemical hydrogen-releasing oxidation coupling
CN114411180B (en) * 2022-03-08 2023-03-21 江西师范大学 Method for constructing sulfur (selenium) substituted phosphate compound by electrochemical hydrogen-releasing oxidation coupling

Also Published As

Publication number Publication date
GB874570A (en) 1961-08-10
DE1071696B (en) 1959-12-24
DK104029C (en) 1966-03-21
FR1237651A (en) 1960-07-29
CH399441A (en) 1965-09-30
BE583685A (en) 1960-02-15

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